KR20060084847A - Polymerizable compositions and molded articles produced by using the same - Google Patents

Abstract

The invention provides polymerizable compositions capable of giving molded articles of crosslinked cycloolefin resins and crosslinked cycloolefin resin composite materials which are excellent in heat resistance; and molded articles produced by using the compositions, more specifically, a polymerizable composition comprising a cycloolefin mixture containing 0.1 to 50 % by mole of a cycloolefin bearing as the substituent a monovalent atomic group having an aliphatic carbon-carbon unsaturated bond, a metathesis polymerization catalyst, and a radical generator; and molded articles produced by using a polymerizable composition described above which preferably further contains a chain transfer agent and making the cycloolefin mixture undergo at least ring- opening polymerization.

Description

Polymerizable composition, and the molded object manufactured using the same TECHNICAL FIELD

The present invention relates to a polymerizable composition containing cycloolefin and a resin molded product obtained by using the same. More specifically, it is possible to provide a crosslinked resin molded article or a crosslinked resin composite material using a cycloolefin resin having excellent heat resistance. It relates to a polymerizable composition and a resin molded article.

It is known that a crosslinked resin molded article is obtained by crosslinking a cycloolefin resin obtained by ring-opening polymerization of cycloolefins such as norbornene in the presence of a metathesis polymerization catalyst with a crosslinking agent such as an organic peroxide. This crosslinked resin molded article is said to have excellent electrical properties such as low dielectric constant and low dielectric loss tangent in addition to mechanical strength and chemical resistance. In view of these characteristics, for example, a solution obtained by dissolving a cycloolefin polymer and a crosslinking agent in a solvent is cast on a flat plate, followed by volatilization of the solvent by heating and crosslinking at the same time to produce a resin molded body on a film. Laminating | stacking on the board | substrate for printed wiring boards etc. to make the electronic component which is a crosslinked resin composite material is proposed. Japanese Patent Application Laid-Open No. 6-248164 discloses a film obtained by casting a thermoplastic hydrogenated ring-opening norbornene-based resin, an organic peroxide, and a norbornene-based resin composition in which a solvent is dissolved in a solvent, followed by casting on a support and drying the composition. The prepreg obtained by impregnating a fiber reinforcement and drying is laminated | stacked on copper foil, pressurized and heated, and the crosslinking resin composite material formed by crosslinking is disclosed. However, the crosslinked resin composite material thus obtained is not sufficiently heat resistant to produce an electronic component using lead-free solder, which has been adopted as an environmental protection measure. Moreover, there exists a problem that a process is cumbersome, such as removing a solvent, in order to obtain a film-form crosslinked resin molded object. On the other hand, Japanese Patent Application Laid-Open No. 11-507962 discloses a ring-opening polymerization of cycloolefin in the presence of a ruthenium carbene complex and a peroxide without a solvent to prepare a cycloolefin polymer, and then postcure (or postcrosslink) to form a crosslinked resin. We are suggesting how to get it.

[Initiation of invention]

As a result of examination by the present inventors, it turned out that the crosslinked resin obtained by the method of the said Unexamined-Japanese-Patent No. 11-507962 also may not acquire sufficient heat resistance.

Then, the objective of this invention is providing the polymeric composition and resin molding which can provide the cycloolefin crosslinked resin molded object and crosslinked resin composite material which were excellent in heat resistance in view of the said prior art problem.

MEANS TO SOLVE THE PROBLEM As a result of continuing earnest research in order to solve the said subject, the resin molding obtained by controlling the kind and quantity of the crosslinking point reacted with the radical generator in the ring-opening polymer of a cycloolefin is obtained. The heat resistance of the crosslinked resin molded body and the crosslinked resin composite material was found to be improved. Further, in addition to the metathesis polymerization catalyst and the radical generator, it was found that the above object is achieved by using a cycloolefin having a specific chemical structure at a specific ratio as the cycloolefin, and completed the present invention based on this finding. It came to the following.

Thus, according to the present invention, the following 1 to 8 are provided.

1. A polymerizable composition comprising a cycloolefin mixture containing 0.1 to 50 mol% of a cycloolefin having a monovalent atomic group having an aliphatic carbon-carbon unsaturated bond as a substituent, a metathesis polymerization catalyst and a radical generator.

2. The polymerizable composition according to 1 above, further comprising a chain transfer agent.

3. The resin molded object obtained by ring-opening-polymerizing the polymeric composition of said 1 or 2.

4. The resin molded body obtained by apply | coating the polymeric composition of said 1 on a support body, and then ring-opening-polymerizing.

5. The resin molded object obtained by inject | pouring the polymeric composition of 1 into the space part of a shaping | molding die, and then ring-opening-polymerizing.

6. A resin molded product obtained by impregnating a polymerizable composition according to 1 to a fibrous reinforcing material and then ring-opening polymerization.

7. Crosslinked resin molded article formed by heating and crosslinking the resin molded article of said 3 to temperature higher than the peak temperature in the said ring-opening polymerization.

8. Crosslinked resin composite material formed by laminating | stacking the resin molding of said 3 on a base material, and then heating and crosslinking.

By this invention, the polymeric composition and resin molding which can provide the crosslinked resin molded object of cycloolefin excellent in heat resistance, and a crosslinked resin composite material are provided.

Best Mode for Carrying Out the Invention

The polymerizable composition of the present invention is a cycloolefin mixture containing 0.1 to 50 mol% of cycloolefins (hereinafter referred to as "specific cycloolefins") having a monovalent atomic group having an aliphatic carbon-carbon unsaturated bond as a substituent, metaceta. It contains a cis polymerization catalyst and a radical generator.

The specific cycloolefin used in the present invention is a monocyclic or polycyclic aliphatic hydrocarbon having a carbon-carbon double bond in a ring, in which a monovalent atomic group having an aliphatic carbon-carbon unsaturated bond is bonded as a substituent.

The monovalent atomic group having an aliphatic carbon-carbon unsaturated bond may be any as long as it has an aliphatic carbon-carbon unsaturated bond, but the carbon number is usually 2 to 30, preferably 2 to 20. It is preferable that an unsaturated bond is a carbon-carbon double bond. Moreover, it is preferable that a carbon-carbon unsaturated bond exists in the chain-shaped hydrocarbon group. Moreover, it is more preferable that a carbon-carbon unsaturated bond exists in the terminal of the said atomic group. The monovalent atomic group which has an aliphatic carbon-carbon unsaturated bond may have a substituent containing a hetero atom.

As the monovalent atomic group having such an aliphatic carbon-carbon unsaturated bond, for example, vinyl group, allyl group, acryloyl group, methacryloyl group, vinyloxy, aryloxy group, vinyloxycarbonyl group, allyloxycarbonyl group, acryloxy Methyl group, methacryloxymethyl group, vinylphenyl group, propenoxycarbonylphenyloxycarbonyl, etc. are mentioned.

In the specific cycloolefin, a cycloolefin ring is incorporated into the polymer by metathesis ring-opening polymerization. When the crosslinking reaction is carried out between the polymers by the radical generator described later, the unsaturated bonding portion of the atomic group in the polymer also crosslinks to form a crosslinking point, so that a crosslinked resin molded article having a high crosslink density can be formed. .

The specific cycloolefin comprises 0.1 to 50 mol%, preferably 0.5 to 40 mol%, more preferably 1 to 30 mol% in the cyclo olefin mixture. When the amount of the specific olefin is too small, the crosslinking density becomes low and sufficient heat resistance is not obtained. When the amount is too large, the mechanical properties of the resin molded body decrease.

Examples of specific cycloolefins include 3-vinyl-1-cyclobutene, 3-vinyl-1-cyclopentene, 3-vinyl-1-cyclohexene, 4-vinyl-1-cyclohexene, 3-methyl-5-vinyl- Monocyclic cyclo olefin compounds such as 1-cyclohexene, 3-cyclohexene-1-carboxylic acid allyl, 3-cyclohexene-1-carboxylic acid vinyl, and 1-methyl-3-cyclohexene-1-carboxylic acid allyl;

5-vinyl-2-norbornene, 5- (2-propenyl) -2-norbornene, 5- (3-butenyl) -2-norbornene, 5- (4-pentenyl) -2-norbornene , 5,6-divinyl-2-norbornene, 5-methyl-6-vinyl-2-norbornene, 5-vinyloxy-2-norbornene, 5-vinyloxymethyl-2-norbornene, 5-aryl Oxy-2-norbornene, 5-aryloxymethyl-2-norbornene, 2-norbornene-5-carboxylic acid vinyl, 2-norbornene-5-carboxylic acid allyl, 2-norbornene-5-carboxylic acid 4-vinylphenyl , 5-methyl-2-norbornene-5-carboxylic acid vinyl, 5-methyl-2-norbornene-5-carboxylic acid allyl, 5-methyl-2-norbornene-5-carboxylic acid 4-vinylphenyl, methacrylic acid 5 Norbornene-2-yl, 5-norbornene-2-yl acrylate, 5-norbornene-2-ylmethyl methacrylate, 5-norbornene-2-ylmethyl acrylate, 2-norbornene-5,6 Dicarboxylic acid divinyl, 2-norbornene-5,6-dicarboxylic acid diallyl, 6-methoxycarbonyl-2-norbornene-5-carboxylic acid vinyl, 6-methoxycarbonyl-2-norbornene-5 -Carboxylic acid allyl, 6-ethoxycarbonyl-2-norbornene-5-carboxylic acid vinyl, 6- Ethoxycarbonyl-2-norbornene-5-carboxylic acid allyl, 2-norbornene-5-carboxylic acid 2-acryloxyethyl, 2-norbornene-5-carboxylic acid 2-methacryloxyethyl, 2- (2-pro Phenoxycarbonyl) benzoic acid 5-norbornene-2-ylmethyl, 2-norbornene-5-carboxylic acid 2,2-di (acryloxymethyl) pentane-4-yl, 5-methyl-2-norbornene- Bicyclic cycloolefin compounds such as 5-carboxylic acid 2,2-di (methacryloxymethyl) pentin-4-yl and methacrylic acid 7-oxa-5-norbornene-2-yl;

N- (4-vinylphenyl) -2-norbornene-5,6-dicarboxyimide, N-allyl-2-norbornene-5,6-dicarboxyimide, 9-vinyltricyclo [6.2.1.0 ^2, Tricyclic cycloolefin compounds such as ⁷ ] undeca-4-ene and 4-vinyltricyclo [6.2.1.0 ^2,7 ] undeca-9-ene;

9-vinyl-4-tetracyclododecene, 9- (2-propenyl) -4-tetracyclododecene, 4-tetracyclododecene-9-carboxylic acid vinyl, 4-tetracyclododecene-9-carboxylic acid allyl And tetracyclic cycloolefins such as 4-tetracyclododecene-9,10-dicarboxylic acid diallyl and the like.

The cycloolefin mixture contains cycloolefins other than the specific cycloolefins mentioned above. As cycloolefin other than a specific cycloolefin, the cycloolefin monomer (norbornene-type monomer or monocyclic cycloolefin monomer) which does not have the monovalent atomic group which has aliphatic carbon-carbon unsaturated bond is used together.

Examples of the norbornene monomers include norbornenes, dicyclopentadienes, tetracyclododecenes, and cyclic olefins having five or more rings. These may have a hydrocarbon group, such as a methyl group, and polar groups, such as a carboxyl group.

Specific examples of norbornenes include bicyclo [2.2.1] hepto-2-ene (hereinafter referred to as 2-norbornene), 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl 2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, 5-cyclohexyl-2-norbornene, 5-cyclopentyl-2-norbornene, 5-ethylidene-2 Norbornene, 5-cyclohexenyl-2-norbornene, 5-cyclopentenyl-2-norbornene, 5-phenyl-2-norbornene, tetracyclo [9.2.1.0 ^2,10 .0 ^3,8 ] Tetradeca-3,5,7,12-tetraene (also referred to as 1,4-methano-1,4,4a, 9a-tetrahydro-9H-fluorene), tetracyclo [10.2.1.0 ^2,11 .0 ^4,9 ] pentadeca-4,6,8,13-tetraene (also called 1,4-methano-1,4,4a, 9,9a, 10-hexahydroanthracene), 2-norbornene -5-Methyl carboxylic acid, 2-norbornene-5-ethyl carboxylic acid, 5-methyl-2-norbornene-5-methyl carboxylic acid, 5-methyl-2-norbornene-5-ethyl carboxylic acid, 5-norbornene- 2-yl, 2-methyl-5-norbornene-2-yl, 5-acrylic acid Norbornene-2-yl, 2-norbornene-5-carboxylic acid, 2-norbornene-5,6-dicarboxylic acid, 2-norbornene-5,6-dicarboxylic acid anhydride, 2-norbornene-5-methanol, 2-norbornene-5,6-dimethanol, 2-norbornene-5,6-dimethanol, 2-norbornene-5-ol, 2-norbornene-5-carbonitrile, 2-norbornene-5- Carbaldehyde, 2-norbornene-5-carboxamide, 5-acetyl-2-norbornene, 6-methoxycarbonyl-2-norbornene-5-carboxylic acid, 2-norbornene-5,6-dicarboxyi Mead, 7-oxa-2-norbornene, 5-methyl-7-oxa-2-norbornene, 5-ethyl-7-oxa-2-norbornene, 5-butyl-7-oxa-2-norbornene, 5-hexyl-7-oxa-2-norbornene, 5-cyclohexyl-7-oxa-2-norbornene, 5-ethylidene-7-oxa-2-norbornene, 5-phenyl-7-oxa-2 Norbornene, 7-oxa-2-norbornene-5-carboxylic acid methyl, acetic acid 7-oxa-5-norbornene-2-yl and the like.

Specific examples of the dicyclopentadienes include dicyclopentadiene, methyldicyclopentadiene, dihydrodicyclopentadiene (tricyclo [5.2.1.0 ^2,6 ] deca-8-ene), and the like. Can be.

Specific examples of the tetracyclododecenes include tetracyclo [6.2.1.1 ^{3,6.0 2,7} ] dodeca-4-ene (hereinafter referred to as 4-tetracyclododecene), 9-methyl-4-tetracyclo Dodecene, 9-ethyl-4-tetracyclododecene, 9-cyclohexyl-4-tetracyclododecene, 9-cyclopentyl-4-tetracyclododecene, 9-methylene-4-tetracyclododecene, 9 -Ethylidene-4-tetracyclododecene, 9-cyclohexenyl-4-tetracyclododecene, 9-cyclopentenyl-4-tetracyclododecene, 9-phenyl-4-tetracyclododecene, 9- Carboxylic acid methyl-4-tetracyclododecene, 9-methyl-9-carboxylic acid methyl-4-tetracyclododecene, 4-tetracyclododecene-9-methanol, 4-tetracyclododecene-9-ol, 4- Tetracyclododecene-9-carboxylic acid, 4-tetracyclododecene-8,9-dicarboxylic acid, 4-tetracyclododecene-8,9-dicarboxyl Anhydride, 4-tetracyclododecene-9-carbonitrile, 4-tetracyclododecene-9-carbaldehyde, 4-tetracyclododecene-9-carboxamide, 4-tetracyclododecene-8,9- Dicarboxylic acid imide, 9-chloro-4-tetracyclododecene, 9-trimethoxysilyl-4-tetracyclododecene, 9-acetyl-4-tetracyclododecene and the like.

Specific examples of the five or more cyclic olefins include pentacyclo [6.5.1.1 ^{3,6 2,7 9,13} ] ^pentadeca -4,10-diene, pentacyclo [9.2.1.1 ^4,7 . 0 ^2,10 .0 ^3,8] deca-penta -5,12- diene, hexa cyclo ^{[6.6.1.1 3,6 .1 10,13 .0 2,7 .0} 9,14] heptadecyl-4-deca Yen etc. are mentioned.

Although these norbornene-type monomers can be used individually by 1 type, 2 or more types can also be used together. It is possible to adjust the glass transition temperature and melting temperature of the molded object obtained by using 2 or more types of monomers together and changing the blend ratio.

Examples of the monocyclic cycloolefin monomers include cyclobutene, cyclopentene, cyclooctene, cyclododecene, 1,5-cyclooctadiene, and the like, and derivatives thereof having polar groups such as carboxyl groups.

When monocyclic cyclo olefin monomers are used, the monocyclic cyclo olefin monomers are contained in the cyclo olefin mixture, preferably at most 40% by weight, more preferably at most 20% by weight. When the amount of the olefin monomer is too large in a monocyclic cycle, the polymer obtained by ring-opening polymerization tends to be an elastomeric phase rather than a resinous phase.

The metathesis polymerization catalyst used in the present invention is not particularly limited as long as it is a metathesis ring-opening polymerization of cycloolefin. As such a metathesis polymerization catalyst, a complex in which a plurality of ions, atoms, polyatomic ions and / or compounds are bonded as transition metal atoms as a central atom is mentioned. Examples of the transition metal atom include atoms of group 5, 6, and 8 of the periodic table (long form type; The atom in each group is not specifically limited, For example, tantalum as an atom of group 5, molybdenum and tungsten as an atom of group 6, ruthenium and osmium are mentioned as an atom of group 8.

Among these, a complex of group 8 ruthenium and osmium is preferable, and a ruthenium carbene complex in which ruthenium carbene is coordinated is particularly preferable for the following reasons. Since ruthenium carbene complex is excellent in catalytic activity, the ring-opening polymerization reaction rate of a polymeric composition can be made high and it is excellent in productivity. Moreover, there is little odor (derived from unreacted cyclic olefin) in the resin molding obtained. In addition, the ruthenium carbene complex is relatively stable against oxygen and moisture in the air, and has a feature that is difficult to deactivate.

Ruthenium carbene complexes are described, for example, in Organic Letters, Vol. 1, p. 953, 1999; Tetrahedron Letters, Vol. 40, p. 2247, 1999, etc.].

Examples of ruthenium carbene complexes include benzylidene (1,3-dimethylimimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3-dimethylimidazolidine- 2-ylidene) (3-methyl-2-butene-1-ylidene) (tricyclopentylphosphine) ruthenium dichloride, benzylidene (1,3-dimethylyl-octahydrobenzimidazol-2-yl Den) (tricyclohexylphosphine) ruthenium dichloride, benzylidene [1,3-di (1-phenylethyl) -4-imidazoline-2-ylidene] (tricyclohexylphosphine) ruthenium dichloride, Benzylidene (1,3-dimethyl-2,3-dihydrobenzimidazole-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (tricyclohexylphosphine) (1,3 , 4-triphenyl-2,3,4,5-tetrahydro-1H-1,2,4-triazole-5-ylidene) ruthenium dichloride, (1,3-diisopropylhexahydro Such as limidine-2-ylidene) (ethoxymethylene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimethyl imidazolidine-2-ylidene) pyridineruthenium dichloride Ruthenium complex compounds in which a hetero atom-containing carbene compound and a neutral electron donating compound are bonded;

Benzylidenebis (1,3-dicyclohexylimidazolidine-2-ylidene) ruthenium dichloride, benzylidenebis (1,3-diisopropyl-4-imidazoline-2-ylidene) ruthenium di Ruthenium complex compounds in which two hetero atom-containing carbene compounds such as chloride are bonded;

(1,3-dimethylimidazolidine-2-ylidene) (phenylvinylidene) (tricyclohexylphosphine) ruthenium dichloride, (t-butylvinylidene) (1,3-diiso Propyl-4-imidazoline-2-ylidene) (tricyclopentylphosphine) ruthenium dichloride, bis (1,3-dicyclohexyl-4-imidazoline-2-ylidene) phenylvinylideneruthenium Dichloride and the like.

The amount of metathesis polymerization catalyst is usually 1: 2,000 to 1: 2,000,000, preferably 1: 5,000 to 1: 1,000,000, more preferably 1: in the molar ratio of "transition metal atom: cycloolefin mixture in catalyst". And 10,000 to 1: 500,000.

The radical generator used in the present invention generates a radical by heating and thereby has a function of crosslinking a cycloolefin polymer. The site where the radical generator causes the crosslinking reaction is mainly a carbon-carbon double bond of the resin constituting the resin molded body, but even a saturated bond portion may sometimes crosslink.

Examples of the radical generator include organic peroxides and diazo compounds. As an organic peroxide, For example, hydroperoxides, such as t-butyl hydroperoxide, p-mentane hydroperoxide, cumene hydroperoxide; Dialkyl peroxides such as dicumyl peroxide and t-butyl cumyl peroxide; Diacyl peroxides such as dipropyl-onyl peroxide and benzoyl peroxide; 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexine-3,1,3-di peroxy ketals such as (t-butyl peroxy isopropyl) benzene; peroxy esters such as t-butyl peroxy acetate and t-butyl peroxy benzoate; peroxy carbonates such as t-butyl peroxy isopropyl carbonate and di (isopropyl peroxy) dicarbonate; Alkyl silyl peroxides, such as t-butyl trimethylsilyl peroxide, etc. are mentioned. Especially, dialkyl peroxide is preferable at the point which has little obstacle to the metathesis polymerization reaction in block polymerization especially.

Examples of the diazo compound include 4,4'-bisazidebenzal (4-methyl) cyclohexanone, 4,4'-diazidechalcone, 2,6-bis (4'-azidebenzal) cyclohexanone , 2,6-bis (4'-azidebenzal) -4-methylcyclohexanone, 4,4'- diazide diphenylsulfone, 4,4'- diazide diphenylmethane, 2,2'- Diazide steel, etc. are mentioned.

The amount of radical generator is usually 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the cycloolefin mixture. When there are too few radical generators, crosslinking will become inadequate and there exists a possibility that the crosslinked resin molded object of a high crosslinking density may not be obtained. On the contrary, when there are too many radical generators, there exists a possibility that the crosslinking resin molded object which may have the physical property of the grade which the crosslinking effect is saturated and is expected may not be obtained.

Various additives can be mix | blended with the polymeric composition of this invention as needed in the range which does not impair the effect of this invention. Examples of such additives include chain transfer agents, activators (cocatalysts), polymerization retardants, crosslinking aids, fillers, solvents, modifiers, antioxidants, flame retardants, colorants, light stabilizers and the like.

By including the chain transfer agent in the polymerizable composition of the present invention, it is possible to prevent the crosslinking reaction due to heat generation during ring-opening polymerization to proceed. The resin molded body which ring-opened-polymerized the polymerizable composition containing a chain transfer agent will become a molten state when heated to high temperature, and a crosslinking reaction will advance at the temperature higher than the maximum temperature (peak temperature) at which ring-opening polymerization advanced, and a crosslinked resin Provide a molded article.

When the high temperature resin molded body is laminated on another base material such as a metal foil and then heated, the resin molded body in a molten state may change along the shape of another base material at an interface with another base material, and the adhesion of the interface is significantly improved. do.

Specific examples of the chain transfer agent include aliphatic olefins such as 1-hexene and 2-hexene; Aromatic olefins such as styrene, vinyl styrene, stilbene, vinyl benzene, and vinyl benzene; Vinyl alicyclic compounds such as vinyl cyclohexane; Vinyl ethers such as ethyl vinyl ether and allyl glycidyl ether; Vinyl ketones such as methyl vinyl ketone; Ethylenically unsaturated esters such as allyl acetate and allyl methacrylate; Alkoxy silanes such as vinyl trimethoxy silane, allyl trimethoxy silane and p-styryl trimethoxy silane; 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 3,3-dimethyl-1,4-pentadiene, 3,5-dimethyl-1,6- Heptadiene, 3,5-dimethoxy-1,6-heptadiene, 1,2-divinyl cyclo hexane, 1,3-divinyl cyclo hexane, 1,4-divinyl cyclo hexane, 1,2-divinyl benzene, 1,3-divinyl benzene, 1,4-divinyl benzene, divinyl cyclopentane, diallyl benzene, divinyl naphthalene, divinyl anthracene, divinyl phenanthrene, trivinyl benzene Hydrocarbon-based chain transfer agents having two or more vinyl groups such as polybutadiene (1,2-addition of 10% or more); Diallyl ether, 1,5-hexadien-3-one, maleic acid diallyl, oxalic acid diallyl, malonic acid diallyl, succinate diallyl, glutaric acid diallyl, adipic acid diallyl, phthalic acid die Allyl, diallyl of fumaric acid, diallyl of terephthalic acid, triallyl of cyanuric acid, triallyl of isocyanuric acid, vinyl ether, allyl vinyl ether, divinyl maleate, divinyl oxalate, divinyl malonate, divinyl succinate, glutaric acid And heteroatom-containing chain transfer agents having two or more vinyl groups such as divinyl, adipic acid divinyl, diphthalic acid divinyl, divinyl fumarate, terephthalic acid divinyl, trivinyl cyanurate, and trivinyl isocyanurate. The amount of the chain transfer agent is usually 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, more preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of the cycloolefin mixture. When the amount of the chain transfer agent is within this range, the crosslinking reaction during the ring-opening polymerization is sufficiently suppressed, so that a resin molded article excellent in fluidity is obtained.

In the case of using a hydrocarbon-based chain transfer agent that does not have a hetero atom such as oxygen, nitrogen, or sulfur among the chain transfer agents having two or more vinyl groups in a molecule, the crosslinked resin molded article or crosslinked resin composite material of the present invention has a relative dielectric constant and dielectric loss tangent. The electrical characteristic values, such as low, become low and it is suitable as an electrical insulation material at the time of handling a high frequency signal. In addition to the compound having two or more vinyl groups in the molecule described above, other chain transfer agents can be used in combination. As another chain transfer agent, the compound which has only one vinyl group is mentioned. The amount of the chain transfer agent having only one vinyl group in the molecule is usually 50 mol% or less, preferably 40 mol% or less, more preferably 30 mol% or less, particularly preferably relative to the chain transfer agent having two or more vinyl groups in the molecule. 10 mol% or less.

An activator (cocatalyst) and a polymerization delay agent are blended for the purpose of controlling the polymerization activity of the metathesis polymerization catalyst or improving the polymerization reaction rate. Examples of the activator include aluminum, scandium, tin, titanium, (partial) alkylates of zirconium, (partial) halides, (partial) alkoxides, and (partial) aryloxylides.

Specific examples of the activator include trialkoxy aluminum, tripenoxy aluminum, dialkoxy alkyl aluminum, alkoxy dialkyl aluminum, trialkyl aluminum, dialkoxy aluminum chloride, alkoxy alkylaluminum chloride, dialkyl aluminum chloride, trialkoxy scandium, tetraalkoxy titanium , Tetraalkoxy tin, tetraalkoxy zirconium and the like.

Examples of the polymerization delay agent include 1,5-hexadiene, 2,5-dimethyl-1,5-hexadiene, (cis and cis) -2,6-octadiene, and (cis and trans)- Chain diene compounds such as 2,6-octadiene and (trans, trans) -2,6-octadiene; (Trans) -1,3,5-hexatriene, (cis) -1,3,5-hexatriene, (trans) -2,5-dimethyl-1,3,5-hexatriene, ( Chain-like triene compounds such as cis) -2,5-dimethyl-1,3,5-hexatriene; Triphenyl phosphine, tri-n-butyl phosphine; Phosphines such as methyl diphenyl phosphine; Lewis bases, such as aniline, etc. are mentioned.

Moreover, cycloolefin which has a diene structure and a triene structure in a ring can be used as a polymerization delay agent. As such cyclo olefin, for example, 1,5-cyclo octadiene, 1,5-dimethyl-1,5-cyclo octadiene, 1,3,5-cyclo peptatriene, (cis, trans, trans) Monocyclic cycloolefins, such as -1,5,9-cyclo dodecatriene, etc. are mentioned. Since cycloolefins having a diene structure or a triene structure in the ring are both a polymerization delay agent and a cycloolefin, it can also function as a polymerization delay agent while being used as part of the cycloolefin mixture.

The amount of the activator and the polymerization delay agent is arbitrarily set according to the compound and the purpose to be used, but is usually 1: 0.05 to 1: 100 in a molar ratio of "transition metal atom in the metathesis polymerization catalyst: activator or polymerization retardant". Preferably it is 1: 0.2-1: 20, More preferably, it is the range of 1: 0.5-1: 10.

The crosslinking aid may be added to the polymerization composition for the purpose of improving the rate of crosslinking reaction. As a crosslinking adjuvant, Dioxime compounds, such as p-quinone dioxime; Methacrylate compounds such as lauryl methacrylate and trimethylol propane trimethacrylate; Fumaric acid compounds such as diallyl fumarate: phthalic acid compounds such as diallyl phthalate, cyanuric acid compounds such as triallyl cyanurate; Imide compounds, such as maleimide, etc. are mentioned. The amount of the crosslinking aid is not particularly limited but is usually 0 to 100 parts by weight, preferably 0 to 50 parts by weight, relative to 100 parts by weight of the cyclo olefin mixture.

The filler is a resin molded article, a crosslinked resin molded article, and a crosslinked resin composite material, which are obtained by ring-opening polymerization of a polymerizable composition, to reduce linear expansion coefficient, to improve mechanical strength such as elastic modulus, to raise dielectric constant, to reduce dielectric loss tangent, and to cure shrinkage. It is contained in a polymeric composition for the purpose of reducing etc.

It is preferable that a filler is particulate form. Specifically, the average particle diameter of the particles calculated from the average of the values obtained by measuring the long diameter of 1000 particles observed with a scanning electron microscope is preferably 0.001 to 100 µm, more preferably 0.01 to 50 µm, particularly preferably 0.1 It is preferable that it is 20 micrometers.

The filler includes an inorganic filler and an organic filler, but in order to achieve the above object, an inorganic filler is preferable. As an inorganic filler, Hydroxides, such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide; Oxides such as silicon oxide (silica), aluminum oxide and zinc oxide; Chlorides such as sodium chloride and calcium chloride; Sulfates such as sodium hydrogen sulfate and sodium sulfate; Nitrates such as sodium nitrate and calcium nitrate; Phosphates such as sodium dihydrogen phosphate and sodium hydrogen phosphate; Silicates such as mica, kaolin, fly ash, talc, mica; Titanate salts such as barium titanate and calcium titanate; Carbides such as silicon carbide and boron carbide; Nitrides such as aluminum nitride, boron nitride and silicon nitride; Glass powder; Carbon black; Metal particles such as aluminum, nickel, magnesium, copper, zinc and iron; Ferrites such as Mn-Mg-Zn-based, Ni-Zn-based and Mn-Zn-based; Ferromagnetic metal powders such as carbonyl iron, iron-silicon-based alloys, iron-aluminum-silicon-based alloys, and iron-nickel-based alloys. Among them (particularly) hydroxides, oxides, titanates and carbonates are preferred, aluminum hydroxide and magnesium hydroxide as hydroxides, silicon oxide (silica) as oxides, barium titanate and calcium titanate as titanates, and calcium carbonate as carbonates. desirable.

As these fillers, those surface-treated with a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, or the like can also be used.

The amount of the filler is usually 1 to 1,000 parts by weight, preferably 100 to 900 parts by weight, more preferably 200 to 800 parts by weight, particularly preferably 300 to 700 parts by weight, based on 100 parts by weight of the cycloolefin mixture. When the amount of the filler is too small, there is a possibility that the low linear expansion rate and the mechanical strength improvement are not sufficiently achieved. On the contrary, when the amount is too large, the mechanical strength of the resin may be lowered.

The addition of the radical crosslinking retardant to the polymerizable composition is preferable because the fluidity and storage stability of the resin molded body can be improved.

Examples of the radical crosslinking retarder include 3-t-butyl-4-hydroxy anisole, 2-t-butyl-4-hydroxy anisole, 3,5-di-butyl-4-hydroxy anisole, 2 Hydroxy anisoles such as, 5-di-t-butyl-4-hydroxy anisole and bis-1,2- (3,5-di-t-butyl-4-hydroxy phenoxy) ethane; Dialkoxy phenols such as 2,6-dimethoxy-4-methylphenol and 2,4-dimethoxy-6-t-butylphenol; Catechols such as catechol, 4-t-butyl catechol, and 3,5-di-t-butyl catechol; Benzoquinones, such as benzoquinone, a naphthoquinone, and methyl benzoquinone, etc. are mentioned. Among these, hydroxy anisoles, catechols and benzoquinones are preferable, and hydroxy anisoles are particularly preferable.

The content of the radical crosslinking retardant is usually 0.001 to 1 mol, preferably 0.01 to 1 mol with respect to 1 mol of the radical generator.

The solvent is used in small amounts in order to dissolve the metathesis polymerization catalyst and the radical generator as necessary. In addition, a solvent can be used as a medium, when carrying out solution polymerization of a polymeric composition. In either case, the solvent must be inert to the catalyst. As such a solvent, For example, Chain aliphatic hydrocarbons, such as n-pentane, n-hexane, n-heptane; Alicyclic hydrocarbons such as cyclopentane, cyclo hexane, methyl cyclo hexane, dimethyl cyclo hexane, hexahydroindene cyclo hexane and cyclo octane; Aromatic hydrocarbons such as benzene, toluene and xylene; Nitrogen-containing hydrocarbons such as nitro methane, nitro benzene and acetonitrile; And oxygen-containing hydrocarbons such as diethyl ether and tetrahydrofuran. Among these, aromatic hydrocarbons, chain aliphatic hydrocarbons, and alicyclic hydrocarbons which are excellent in solubility of the catalyst and industrially used are preferred. In addition, as long as the activity of the metathesis polymerization catalyst is not lowered, a liquid antioxidant, a liquid plasticizer, and a liquid modifier can be used as the solvent.

Examples of the modifier include natural rubber, polybutadiene, polyisoprene, styrene-butadiene copolymers, styrene-butadiene-styrene block copolymers, styrene-isoprene-styrene copolymers, and acrylics. Ronitrile-butadiene-styrene copolymer, acrylonitrile-butadiene copolymer, ethylene-propylene-diene terpolymer, ethylene-vinyl acetate copolymer, polysulfur-based synthetic rubber, acrylic rubber, urethane rubber And elastomers such as fluorine rubber, silicone rubber, polyester elastomer, polyolefin thermoplastic elastomer, and polyvinyl chloride thermoplastic elastomer.

As antioxidant, antioxidants for various plastics and rubbers, such as a phenol type, phosphorus type, an amine type, etc. are mentioned, for example. These antioxidants can be used alone or in combination of two or more thereof.

The polymerizable composition of the present invention is a cycloolefin mixture containing 0.1 to 50 mol% of a cycloolefin having a monovalent atomic group having an aliphatic carbon-carbon unsaturated bond as a substituent, a metathesis polymerization catalyst and a radical generator, and preferably Is obtained by mixing a chain transfer agent, and the above-mentioned additives which are also blended as required. The device, means and order for mixing the polymerizable composition are not particularly limited.

The resin molded object of this invention is obtained by ring-opening-polymerizing the said polymeric composition. The ring-opening polymerization of the polymerizable composition is carried out by a bulk polymerization method or a solution polymerization method, preferably by a bulk polymerization method.

Although there is no restriction | limiting in the method of ring-opening-polymerizing the polymeric composition of this invention and obtaining the said resin molded object, For example, the method of apply | coating (a) a polymeric composition on a support body, and then ring-opening-polymerizing (b) molding a polymeric composition The method of inject | pouring into the space part of a frame, and then ring-opening-polymerizing, (c) the polymeric composition is impregnated in a fibrous reinforcement, and then ring-opening-polymerizing is mentioned.

Since the polymerizable composition of the present invention has a low viscosity, it is possible to smoothly apply the coating in the method of (a), and the injection in the method of (b) can be performed quickly without foaming even if the space is a complicated shape. It is possible to proceed, and in the method of (c), the fibrous reinforcement can be impregnated quickly and seamlessly.

According to the method of (a), resin molded objects, such as a film form and a plate form, are obtained. The thickness of the molded body is usually 15 mm or less, preferably 10 mm or less, and more preferably 5 mm or less.

Examples of the support include films and plates made of resins such as polyethylene terephthalate, polypropylene, polyethylene, polycarbonate, polyethylene naphthalate, polyallylate and nylon; The film, board | plate, etc. which consist of metal materials, such as iron, stainless steel, copper, aluminum, nickel, chromium, gold, and silver, are mentioned. Among them, the use of a metal foil or a resin film is preferable. The thickness of these metal foils or resin films is usually 1 to 150 µm, preferably 2 to 100 µm, and more preferably 3 to 75 µm from the viewpoint of workability and the like.

As an example of the method of apply | coating the polymeric composition of this invention on a support body, well-known coating methods, such as a spray coating method, the dip coating method, the roll coating method, the curtain coating method, the die coating method, the slit coating method, are mentioned. .

The polymerizable composition applied on the support is dried as necessary, followed by ring-opening polymerization. The polymerizable composition is heated for ring-opening polymerization. As a heating method, the method of loading the polymeric composition apply | coated to the support body on a heating plate, heating, the method of heating (heat press), pressurizing using a press machine, the method of pressing the heated roller, the method of using a heating furnace, etc. Can be mentioned.

The shape of the resin molded object obtained by the method of (b) can be set with a shaping | molding die, For example, a film form, columnar shape, other arbitrary three-dimensional image etc. are mentioned.

The shape, material, size, etc. of the molding die are not particularly limited. As such a molding die, a conventionally known molding die, for example, a molding die having a split wood structure, that is, a core type and a cavity type; Molding molds and the like provided with spacers between two plates can be used.

The pressure (injection pressure) for injecting the polymerizable composition of the present invention into the space portion (cavity) of the mold is usually 0.01 to 10 MPa, preferably 0.02 to 5 MPa. If the injection pressure is too low, the filling becomes insufficient, and there is a fear that the transfer of the transfer surface formed on the inner surface of the cavity may not be performed satisfactorily. If the injection pressure is too high, the usable molding die is high in rigidity and is not economical. . The clamping pressure is usually in the range of 0.01 to 10 MPa.

The ring-opening polymerization can be carried out by heating the polymerizable composition filled in the space. As a heating method of a polymeric composition, the method of using heating means, such as a heater and steam provided in a shaping | molding die, the method of heating a shaping | molding die in an electric furnace, etc. are mentioned.

As a resin molding obtained by the method of (c), the prepreg etc. in which the ring-opening polymer is filled in the space | gap of a fibrous reinforcement is mentioned, for example. As the fibrous reinforcing material, inorganic and / or organic fibers may be used, and for example, glass fibers, metal fibers, ceramic fibers, carbon fibers, aramide fibers, polyethylene terephthalate fibers, vinylon fibers, polyester fibers, amide fibers, and the like. Known ones may be mentioned. These can be used individually by 1 type or in combination of 2 or more types. As a shape of a fibrous reinforcement material, a mat, a crossing, a nonwoven fabric, etc. are mentioned.

In order to impregnate the polymerizable composition of the present invention in the fibrous reinforcing material, for example, a predetermined amount of the polymerizable composition is poured over a cross, a mat or the like made of fibrous reinforcing material, and a protective film is laminated thereon as necessary, and the upper side is It can be carried out by pressing (rubbing hard) with a roller. After the fibrous reinforcing material is impregnated with the polymerizable composition, the prepreg in which the polymer is impregnated can be obtained by heating the impregnated substance to a predetermined temperature and ring-opening polymerization. As a heating method, for example, the impregnated substance is installed on a support and heated in the same manner as in the method of (a). After the fibrous reinforcing material is set in the mold in advance, the polymerizable composition is impregnated and then the method of (b). A heating method and the like are used in this manner.

In any of the above methods (a), (b) and (c), the heating temperature (mold temperature in the method of (b)) for ring-opening polymerization of the polymerizable composition is usually 30 to 250 ° C, preferably Preferably it is 50-200 degreeC. The polymerization time is preferably selected appropriately, but is usually 10 seconds to 20 minutes, preferably 30 seconds to 5 minutes.

The ring-opening polymerization reaction starts by heating the polymerizable composition to a predetermined temperature. When the ring-opening polymerization reaction starts, the temperature of the polymerizable composition rises rapidly by the heat of reaction and reaches the peak temperature in a short time (for example, about 10 seconds to about 5 minutes). In addition, the polymerization proceeds, but as the polymerization proceeds gradually, the temperature decreases. When the peak temperature is controlled to be equal to or higher than the glass transition temperature of the resin constituting the resin molded body obtained by this polymerization reaction, polymerization is preferably performed completely. The peak temperature can be controlled by the heating temperature. Moreover, in the case of the resin molded object obtained when mix | blending and superposing | polymerizing a chain transfer agent, the polymerization reaction rate of a resin molded object is 80% or more normally, Preferably it is 90% or more, More preferably, it is 95% or more. On the other hand, the polymerization reaction rate of the resin molded body can be calculated | required, for example by analyzing by gas chromatography the solution obtained by melt | dissolving a resin molded body in a solvent. The resin molded body in which the polymerization almost proceeded has few residual monomers, and therefore has no odor.

When the peak temperature at the time of a ring-opening polymerization reaction becomes high, there exists a possibility that not only a ring-opening polymerization reaction but a crosslinking reaction may advance also at once. Therefore, in order to fully advance the ring-opening polymerization reaction and prevent the crosslinking reaction from proceeding, the peak temperature of the ring-opening polymerization should preferably be controlled to less than 200 ° C.

In this case, it is preferable to make the peak temperature in ring-opening polymerization below 1 minute half life temperature of a radical generator. Here, the half-life temperature for 1 minute is the temperature at which half of the radical generator decomposes for 1 minute. For example, it is 186 ° C in di-t-butylperoxide and 194 ° C in 2,5-dimethyl-2,5-di (t-butylperoxy) hexin-3.

The crosslinked resin molded article of the present invention can be obtained by heating and crosslinking the above-mentioned resin molded article. The temperature at the time of heating and crosslinking a resin molded object is 170-250 degreeC normally, Preferably it is 180-220 degreeC. It is preferable that this temperature is higher than the peak temperature in the said ring-opening polymerization, and it is more preferable that it is 20 degreeC or more. The time for heating and crosslinking is not particularly limited, but is usually several hours from water.

The method of heating and crosslinking the resin molded product of the present invention is not particularly limited. When a resin molded object is a film form, the method of laminating | stacking several as needed and heating by hot press is preferable. The pressure at the time of hot pressing is usually 0.5-20 MPa, Preferably it is 3-10 MPa.

The crosslinked resin composite material of the present invention is produced by laminating the resin molded article of the present invention on a base material, followed by heating and crosslinking.

As said base material, Metal foil, such as steel foil, aluminum foil, nickel foil, chromium foil, gold foil, silver foil; A printed circuit board manufacturing substrate; And resin films such as polytetrafluoroethylene (PTFE) film and conductive polymer film. The surface of the base material may also be treated with a silane coupling agent, a thiol coupling agent, a titanate coupling agent, various adhesives, or the like. When manufacturing a resin molded object by the method of said (a), a crosslinked resin composite material can be obtained by using a support as a base material as it is, and heating and crosslinking.

The crosslinked resin molded article of the present invention can also be obtained at once (without passing through a resin molded article) using the polymerizable composition. In order to obtain it at once, the ring-opening polymerization temperature of the polymerizable composition is set high and heated to a temperature at which the crosslinking reaction occurs. However, when manufacturing a crosslinked resin composite material, the peeling strength of an interface becomes larger in the one which passes through the step of a resin molding once. Moreover, the crosslinked resin composite material of the present invention has an advantage of being very simple to manufacture because the step of volatizing a solvent such as a conventional casting method is unnecessary.

Although there is no restriction | limiting in the heating method for manufacturing the crosslinked resin composite material of this invention, The method of laminating and heat-pressing a resin molded object and base materials, such as a metal foil and a board | substrate for printed wiring board manufacture, is preferable at the point which has high productivity. The conditions of a hot press are the same as the case of manufacturing the said crosslinked resin molded object.

For example, the resin molded object of this invention and the metal foil as a base material are laminated | stacked, and it can crosslink by heating by a hot press etc., and the metal foil covered laminated board which closely adhered to the metal foil can be obtained. The peeling strength of the metal foil of the obtained metal foil covered laminated board is a value measured according to JIS C6481, when copper foil is used as metal foil, Preferably it is 0.8 kN / m or more, More preferably, it is 1.2 kN / m or more.

The crosslinked resin molded article and the crosslinked resin composite material obtained by using the polymerizable composition or the resin molded article of the present invention are provided with the characteristics of conventional cycloolefin resins such as low linear expansion rate, high mechanical strength, and low dielectric loss tangent as they are. As mentioned above, it is excellent in heat resistance and adhesiveness compared with the conventional cycloolefin resin.

The crosslinked resin molded article and the crosslinked resin composite material according to the present invention having such characteristics include prepregs; Copper foil with resin; It is suitable as an electronic component material such as a printed wiring board, an insulating sheet, an interlayer insulating film, an overcoat, and an antenna substrate.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. The test and evaluation in an Example and a comparative example followed the content mentioned later.

(1) weight average molecular weight (Mw)

The resin part of the prepreg was dissolved in tetrahydrofuran, and Mw of the polymer in the resin molded body was obtained by measuring the weight average molecular weight (Mw) of polystyrene conversion by gel permeation chromatography (GPC).

(2) glass transition temperature (Tg)

The glass transition point temperature (degreeC) was measured with the differential scanning calorimeter based on JISC6481 about the sample extract | collected from the resin part of the laminated board on which single side | surface copper foil was covered.

(3) heat resistance

The resin part of the laminated board with which copper foil was covered on one side was suspended in the solder bath of 280 degreeC for 20 second, the heat resistance test was performed according to JISC 6481, and the following references | standards evaluated.

(Circle): There is no swell.

(Triangle | delta): There exists a swelling slightly.

X: There is swelling.

(4) survival rate

The copper foil of the laminated sheet covered with copper foil on one side was removed by etching with an aqueous solution of ammonium persulfate, and the original plate having a diameter of 10 mm was cut out from the remaining plate, immersed in toluene at 23 ° C. for 24 hours, and taken out with a vacuum dryer. It dried at 5 degreeC for 5 hours, and the ratio (residual ratio) with respect to the weight before toluene dipping of the weight after drying is calculated | required. A crosslinked resin molded article having a large ratio means a large crosslinking density.

EXAMPLE 1

In a 30 ml glass bottle, 42 mg of 3,5-di-t-butylhydroxyanisole (antioxidant) and tetracyclo [6.2.1.1 ^{3,6.0 2,7} ] dodeca-4-ene were 11.3. g (0.04 mole), 2-norbornene to 3.7 g (0.004 mole), 5-vinyl-2-norbornene to 0.45 g, a mixture of divinyl benzene (purity 55%, m-, p-, Tokyo) Kasei products, containing ethyl vinyl benzene and diethyl benzene as impurities, at 0.30 g, di-t-butyl peroxide (half-life temperature of 186 ° C. for 1 minute) at 0.22 ml, and benzyl at 0.05 mol / liter concentration. 0.06 ml of lidene (1,3-dimethylimidazolidine-2-ylidene) (tricyclo hexyl phosphine) ruthenium dichloride / toluene solution (containing 0.25 mol / liter triphenyl phosphine) It was added and stirred to prepare a polymerizable composition.

Glass cross of 200mm in length, 200mm in width, 0.174mm in thickness (product number 7628 / AS891AW, Asahi) on glass fiber reinforced PTFE resin film (product number 5310, product made by Sangoban, Norton) of 300mm in length, 300mm in width, 0.08mm in thickness 2 sheets of Shuebel company) were laid, and the said polymeric composition was poured on it. Next, another sheet of glass fiber reinforced polytetrafluoroethylene resin film as described above was covered thereon, and the polymerizable composition was impregnated using a roller.

The laminated body which interposed the upper and lower parts of the said impregnation with the glass fiber reinforced PTFE resin film was stuck to the hotplate heated at 145 degreeC for 1 minute, and was polymerized. Next, the upper and lower glass fiber reinforced PTFE resin film was peeled off, and the prepreg which is a resin molded object was obtained.

One drop of acetic acid was added to 60 g of distilled water in a glass vessel, 0.18 g of styryl trimethoxy silane (KEM-1403, manufactured by Shin-Etsu Chemical Co., Ltd.) was added thereto, stirred for 1 hour, and dissolved by hydrolysis. This silane coupling agent solution was included in the cotton wool, it was apply | coated to the rough surface of the electrolytic copper foil (roughening GTS process product, Furukawa Circuit Foil company make) of thickness 0.018mm, and it dried at 130 degreeC under nitrogen atmosphere for 1 hour.

Three samples cut to 87 mm in length and 87 mm in width from the prepreg are cut out, and left in the state interposed between the electrolytic copper foil (the surface in contact with the prepreg is rough) and a PTFE film having a thickness of 0.05 mm. The inside dimension was put into the letter-shaped rim of 90 degree long and 90 mm horizontal in 1 mm of thickness, and it hot-pressed at press pressure 4.1 MPa and 200 degreeC for 15 minutes. Then, it cooled, falling a press pressure, and when it became 100 degrees C or less, the sample was taken out and the laminated board in which the copper foil was covered on the single side | surface which is a crosslinked resin composite material was obtained.

The evaluation result of the glass transition temperature (Tg), heat resistance, and the residual ratio of the crosslinked resin in the crosslinked resin molding which comprises the weight average molecular weight (Mw) of the polymer in a prepreg, and the laminated board with which copper foil was covered on one side is written in Table 1.

EXAMPLE 2

In Example 1, it carried out similarly to Example 1 except having set the quantity of 5-vinyl-2- norbornene to 0.75 g (0.00625 mol). The test results in the same manner as in Example 1 are shown in Table 1.

[Comparative Example 1]

In Example 1, it carried out similarly to Example 1 except not adding 5-vinyl-2- norbornene. The test results in the same manner as in Example 1 are shown in Table 1.

As shown in Table 1, the crosslinked resin molded body which comprises the laminated board by which copper foil was covered by the single side | surface which is a crosslinked resin composite material obtained using the polymeric composition of this invention was excellent in heat resistance. Since such a crosslinked resin molded article has a glass transition point, it was found that it is a crosslinked product of a thermoplastic resin, and that the crosslinking density is high because the residual ratio is large (Examples 1 and 2).

On the other hand, the crosslinked resin molded body constituting the crosslinked resin composite material obtained by using a polymerizable composition which does not add cycloolefin (specific cycloolefin) having a monovalent atomic group containing a carbon-carbon unsaturated bond as a substituent has heat resistance. Lagged behind. This crosslinked resin molded article was found to have a low crosslinking density due to its low residual ratio (Comparative Example 1).

Claims (8)

A polymerizable composition comprising a cycloolefin mixture containing 0.1 to 50 mol% of a cycloolefin having a monovalent atomic group having an aliphatic carbon-carbon unsaturated bond as a substituent, a metathesis polymerization catalyst, and a radical generator. The method of claim 1, A polymerizable composition, further comprising a chain transfer agent. The resin molded product obtained by ring-opening-polymerizing the polymeric composition of Claim 1 or 2. A resin molded product obtained by applying the polymerizable composition according to claim 1 on a support and then ring-opening polymerization. The resin molded product obtained by ring-opening-polymerizing after inject | pouring the polymeric composition of Claim 1 into the space part of a shaping | molding die. A resin molded product obtained by impregnating a polymerizable composition according to claim 1 in a fibrous reinforcing material and then ring-opening polymerization. A crosslinked resin molded article obtained by heating and crosslinking the resin molded article according to claim 3 to a temperature higher than the peak temperature in the ring-opening polymerization. The crosslinked resin composite material formed by laminating | stacking the resin molding of Claim 3 on a base material, and then heating and crosslinking.